The present invention relates to triazinic compounds.
More particularly, the present invention relates to novel compounds derivatives of 2,4,6-triamino-1,3,5-triazine, which are capable of endowing the thermoplastic polymers, or the polymers with elastomeric properties, in particular olefinic polymers of copolymers, with high self-extinguishing characteristics, when said polymers are exposed to a flame.
In particular, the subject matter of the present invention are triazinic compounds having the general formula (I): ##STR2## t is either 0 or 1;
when t is equal to 0:
at least one of the radicals from R to R.sub.3 is: ##STR3## wherein: n=an integer within the range of from 2 to 8;
m=an integer within the range of from 2 to 6; PA1 R.sub.5 =H; (C.sub.1 -C.sub.8)-alkyl; (C.sub.2 -C.sub.6)-alkenyl; C.sub.p H.sub.2p O-R.sub.6, wherein p is an integer comprised within the range of from 1 to 4 and R.sub.6 is either H or a (C.sub.1 -C.sub.4)-alkyl; (C.sub.6 -C.sub.12)-cycloalkyl or (C.sub.6 -C.sub.12)-alkylcycloalkyl; PA1 m=an integer within the range of from 2 to 6; PA1 R.sub.5 =H; (C.sub.1 -C.sub.8)-alkyl; (C.sub.2 -C.sub.6)-alkenyl; C.sub.p H.sub.2p O-R.sub.6, wherein p is an integer comprised within the range of from 1 to 4 and R.sub.6 is either H or a (C.sub.1 -C.sub.4)-alkyl; (C.sub.6 -C.sub.12)-cycloalkyl or (C.sub.6 -C.sub.12)-alkylcycloalkyl; PA1 (a) with a number of moles lower than, or equal to (2+w) or an amine of general formula (II), at a temperature comprised within the range of from 40.degree. to 80.degree. C. in order to yield the intermediate of general formula (VIII): ##STR21## wherein Z.sub.2 is hydrogen or ##STR22## and its meaning can vary inside each repeating unit; which intermediate, once again either separated or not, is reacted with a number of moles lower than, or equal to (2+w) of an amine of general formula (IV), at a temperature comprised within the range of from 80.degree. to 150.degree. C. and under similar conditions as those disclosed hereinabove; or PA1 (b) with a number of moles lower than, or equal to 2(2+w) of an amine of general formula (II), at a temperature comprised within the range of from 80.degree. to 150.degree. C., under similar conditions as disclosed hereinabove.
the group: ##STR4## is replaced by a heterocyclic radical bonded to the alkyl chain through the nitrogen atom, and optionally containing another heteroatom preferably selected from among O, S, N; or in general formula (I) at least one of the moieties: ##STR5## is replaced by a heterocyclic radical linked to the triazinic ring through the nitrogen atom and optionally containing another heteroatom preferably selected from the group consisting of O, S N; the other radicals from R to R:, which are either equal to, or different from one another, and can have different meanings in each triazinic ring, have the abovesaid meaning, or they are: H; (C.sub.1 -C.sub.18)-alkyl; (C.sub.2 -C.sub.8)-alkenyl; (C.sub.6 -C.sub.16)-cycloalkyl or (C.sub.6 -C.sub.16)-alkylcycloalkyl, optionally substituted with a hydroxy or (C.sub.1 -C.sub.C.sub.4)-hydroxyalkyl function;
when t is equal to 1 the radicals from R to R.sub.3, which are either equal to, or different from one another, and can have different meanings in each triazinic ring are: H; (C.sub.1 -C.sub.18)-alkyl; (C.sub.2 -C.sub.8)-alkenyl; (C.sub.6 -C.sub.16)-cycloalkyl or (C.sub.6 -C.sub.16)-alkylcycloalkyl, optionally substituted with a hydroxy or (C.sub.1 -C.sub.4)-hydroxyalkyl function; ##STR6## wherein: n=an integer within the range of from 2 to 8;
the radicals R.sub.7, which can be either equal to, or different from one another, are: H; (C.sub.1 -C.sub.8)-alkyl; (C.sub.2 -C.sub.6)-alkenyl; (C.sub.6 -C.sub.12)-cycloalkyl or (C.sub.6 -C.sub.12)-alkylcycloalkyl; (C.sub.1 -C.sub.4)-hydroxyalkyl; or the moiety: ##STR7## is replaced by a heterocyclic radical linked to the alkyl chain through the nitrogen atom and optionally containing another heteroatom preferably selected from the group consisting of O, S, N; or in general formula (I) at least one of the moieties: ##STR8## is replaced by a heterocyclic radical linked to the triazinic ring through the nitrogen atom and optionally containing another heteroatom preferably selected from the group consisting of O, S, N; R.sub.4 is either hydrogen or (C.sub.-C.sub.4)-alkyl; the indexes g, which can be either equal to, or different from, each other, are integers comprised within the range of from 2 to 5; s is an integer within the range of from 2 to 4; w is an integer within the range of from 1 to 5; Z is a hydrogen atom or: ##STR9## and its meaning can vary inside each repeating unit. Belonging to compounds of general formula (I) are also those derivatives having asymmetrical structure in that the radical from R to R.sub.3 can have different meanings in each triazinic ring.
Examples of radicals from R to R.sub.3 in the above general formula (I) are: methyl; ethyl; propyl; isopropyl; n-butyl; isobutyl; tert-butyl; n-pentyl; isopentyl; n-hexyl; tert-hexyl; octyl; tert-octyl; decyl; dodecyl; octadecyl; ethenyl; propenyl; butenyl; isobutenyl; hexenyl; octenyl; cyclohexyl; propylcyclohexyl; butyl cyclohexyl; decyl cyclohexyl; idroxycyclohexyl; idroxyethyl cyclohexyl; 2-hydroxyethyl; 2-hydroxypropyl; 3-hydroxypropyl; 3-hydroxybutyl; 4-hydroxybutyl; 3-hydroxypentyl; 5-hydroxypentyl; 6-hydroxyhexyl; 3-hydroxy-2,5-dimethyl hexyl; 7-hydroxyheptyl; 7-hydroxyoctyl; 2-methoxy ethyl; 2-methoxy propyl; 3-methoxy propyl; 4-methoxy butyl; 6-methoxy hexyl; 7-methoxyheptyl; 7-methoxy octyl; 2-ethoxy ethyl; 3-ethoxy propyl; 4-ethoxy butyl; 3-propoxy propyl; 3-butoxy propyl; 4-butoxy-butyl; 4-isobutoxy butyl; 5-propoxy pentyl; 2-cyclohexyloxyethyl; 2-ethenyloxy ethyl; 2-(N,N-dimethylamino)ethyl; 3-(N,N-dimethylamino)propyl; 4-(N,N-dimethylamino)butyl; 5-N,N-dimethylamino)pentyl; 4-(N,N-diethylamino)butyl; 5-(N,N-diethylamino)pentyl; 5-(N,N-di-isopropylamino)pentyl; 3-(N-ethylamino)propyl; 4-(N-methylamino)butyl; 4-(N,N-dipropylamino)butyl; 2-(N,N-diisopropylamino)ethyl; 6-(N-hexenylamino)hexyl; 2-(N-ethenylamino)ethyl; 2-(N-cyclohexylamino)ethyl; 2-(N-2-hydroxyethylamino)ethyl; 2-(2-hydroxyethoxy)ethyl; 2-(2-methoxyethoxy)ethyl; and so forth.
Examples of heterocyclic radicals which can replace the moieties: ##STR10## are: aziridine; pyrrolidine; piperidine; morpholine; thiomorpholine; piperazine; 4-methyl piperazine; 4-ethylpiperazine; 2-methyl piperazine; 2,5-dimethyl piperazine; 2,3,5,6-tetramethyl piperazine; 2-ethyl piperazine; 2,5-diethyl piperazine; and so forth.
Triazinic compounds according to the present invention are also those on which the moieties: ##STR11## are substituted by a heterocyclic radical selected from among the following: aziridine; pyrrolidine; piperidine; morpholine; thiomorpholine; piperazine; 4-methyl piperazine; 4-ethylpiperazine; and so forth.
Examples of polyvalent radicals ##STR12## are those which derive, by elimination of a hydrogen atom from each reacted amino group, from the following polyaminic compounds: bis(2-aminoethyl)amine; bis(3-aminopropyl)amine; bis(4-aminobutyl)amine; bis(5-aminopentyl)amine; bis[2-(N-methylamino)ethyl]amine; 2-N-butyl bis(2-aminoethyl)amine; bis[3-(N-methylamino)propyl]-amine; N-(3-aminopropyl)-1,5-diamino pentane; N-(4-aminobutyl)-1,5-diamino pentane; tris(2-aminoethyl)amine; tris(3-aminopropyl)amine; tris(4-aminobutyl)amine; tris[2-(N-ethylamino)ethyl]amine; N,N'-bis(2-aminoethyl)-1,2-diamino ethane; N,N'-bis(3-aminopropyl)-1,3-diaminopropane; N,N'-bis(2-aminoethyl)-1,3-diamino propane; N,N'-bis(3-aminopropyl)-1,2-diamino ethane; N,N'-bis(3-aminopropyl-1,4-diaminobutane; bis[2-(2-aminoethyl)-aminoethyl]amine; N,N' bis-[2-(2-aminoethyl)aminoethyl]-1,2-diamino ethane; N,N,-bis[3-(2-aminoethyl) aminopropyl]-1,2-diamino ethane; N,N,N',N'-tetrakis(2-aminoethyl)-1,2-diamino ethane; and so forth.
Specific compounds comprised within the scope of general formula (I) are reported in the examples which follow the instant disclosure.
The compounds of general formula (I) can be prepared by reacting, at temperatures comprised within the range of from 0.degree. to 10.degree. C., and at a pH value comprised within the range of from 5 to 7, a halide of cyanuric acid, such as, e.g., cyanuric chloride, in a suitable solvent (such as, e.g., acetone, water, methylene chloride, and so forth) with an amine having the general formula (II): ##STR13## wherein R and R.sub.1 have the hereinabove defined meaning, in the presence or less (according to the molar ratio used in the reaction) of an acid acceptor (such as, e.g., NaOH, NaHCO.sub.3, Na.sub.2 CO.sub.3, triethylamine, and so forth) with the intermediate (III): ##STR14## being obtained.
Such an intermediate, either separated or not separated from the reaction mixture, is subsequently reacted under conditions similar to those as hereinabove specified, but operating at a temperature comprised within the range of from 10.degree. to 50.degree. C. and an amine of general formula (IV): ##STR15## wherein R.sub.2 and R.sub.3 have the hereinabove defined meaning, with the intermediate (V): ##STR16## being obtained.
The intermediate (V), either separated or not and in a number of moles smaller than, or equal to, (2+w), is reacted in its turn, under the same conditions as of the two first reaction steps, but operating at higher temperature than of the preceding step, e.g., comprised within the range of from 70.degree. to 150.degree. C. and hence with a solvent being used which is compatible with such temperature values (such as, e.g., water, toluene, xylene, dimethylformamide, and so forth), with one mole of a polyamine having the general formula (VI): ##STR17## wherein R.sub.4, q, s, t, and w have the same meaning as defined hereinabove, with the compounds of general formula (I) being obtained as the end products.
In case compounds of general formula (I) containing equal moieties ##STR18## are desired, the process is carried out by reacting cyanuric chloride with two moles of an amine of general formula (II) under the same conditions as disclosed hereinabove in order to obtain the intermediate of general formula (V).
An alternative method consists of reacting a number of moles lower than, or equal to, (2+w) of a halide, such as, e.g., the chloride, of cyanuric acid with one mole of a polyamine of general formula (VI) as above defined, still under the same conditions as hereinabove disclosed, at a temperature comprised within the range of from 0.degree. to 10.degree. C. in order to yield the intermediate of general formula (VII): ##STR19## wherein Z is hydrogen or: ##STR20## and its meaning can vary inside each repeating unit.
Such an intermediate, either separated or not, is reacted once again:
Good quality products of general formula (I) are generally obtained as a white crystalline powder, which can be used in the self-extinguishing polymeric compositions without further purifications.